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Ag/TiO2 and Ag/SiO2 composite spheres with coreshell structures were synthesized via an ion-exchange
method. Thin layers of TiO2 or SiO2 are deposited onto CaMg(CO3)2 templates using tetrabutyl titanate or
tetraethoxysilane, respectively, and the CaMg(CO3)2 cores are subsequently replaced by Ag2CO3 based on
the solubility product constant gap, followed by calcination of the intermediates, resulting in Ag/TiO2 and
Ag/SiO2 composite particles. The samples were characterized by X-ray powder diffraction (XRD), scanning
Received 2nd February 2013,
Accepted 22nd April 2013
electron microscopy (SEM), thermogravimetry analysis (TGA), Fourier transform infrared spectroscopy (FT-
IR) and energy dispersive X-ray spectroscopy (EDX). The amount of Ag nanoparticles in the composites can
DOI: 10.1039/c3ra40596f
be adjusted using the relative concentration of the AgNO3 solution. Both the Ag/TiO2 and Ag/SiO2
www.rsc.org/advances composites exhibit excellent antibacterial activities using E. coli and S. aureus as test bacterial spawn.
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Antibacterial testing
The antimicrobial activities of the Ag/TiO2 and Ag/SiO2
composite spheres were analyzed by inhibition zone testing
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9740 | RSC Adv., 2013, 3, 97399744 This journal is The Royal Society of Chemistry 2013
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N2
2Ag2 CO3 4Agz2CO2 zO2 (III)
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Fig. 3 Field emission scanning electron microscopic (FESEM) images of the Ag/ Fig. 4 SEM (a, c and d) and EDX (b) images of the Ag/TiO2 composite spheres
TiO2 composite spheres (ad). The insets in (b) and (d) are EDX spectra. obtained with different reaction times: (a) and (b) 2 h, (c) 4 h, (d) 8 h.
The effect of synthesis factors on the structure of the The calcination temperature is also an important factor in
composites the preparation of the materials. In the XRD patterns of the
samples obtained at different reaction temperatures (Fig. S10,
In order to investigate the ion-exchange reaction, some
ESI3), all of the peaks are in good agreement with the Ag NPs/
influencing factors were considered. The reactant concentra-
TiO2 composite. A sample with good crystallization and an
tion is an important factor in the preparation of composite integrated spherical morphology can be obtained after
materials, especially for those with hybrid structures. In the calcination at 400 uC. However, there is much fragmentation
process of these experiments, the effect of changing the Ag+ in the composite when the temperature is increased to 600 uC
concentration on the structure, morphology and properties (Fig. S11, ESI3).
was investigated. Fig. S7, ESI,3 shows the XRD patterns of the
samples obtained with different Ag+ concentrations. There is Antibacterial properties
no variation in the peak positions of the Ag NPs, but the To evaluate the antibacterial activity of the Ag/TiO2 and Ag/
intensity decreases with increasing Ag+ concentration. The SiO2 composite spheres, inhibition zone experiments were
reason may be that the crystallite dimensions are larger at carried out with the Gram-negative bacteria Escherichia coli
lower concentrations. This phenomenon can also be observed and the Gram-positive bacteria Staphylococcus aureus (Fig. 5
in the SEM images in Fig. S8 in the ESI.3 There is also a large and 6). The relationship between antibacterial properties and
amount of inhomogeneous Ag NPs outside the TiO2 shell (Fig. concentration was investigated using the Ag/TiO2 composite
S8a, ESI3). This result confirms that the reaction rate may slow spheres. As shown in Fig. S12 in the ESI,3 whether Gram-
down when the reactant concentration decreases. negative or Gram-positive bacteria are used, the Ag/TiO2
In order to further investigate the effect of reaction time on composite spheres show better antimicrobial activity to some
the products, the reaction was controlled from 2 h to 8 h. Fig. 4 extent. From the images and data, the diameter of the
and Fig. S9, ESI,3 show the SEM images and EDX spectra of inhibition zone decreases from 11 mm to 9 mm when the
products obtained at different reaction times. There was a concentration of Ag/TiO2 composite spheres decreases from
large amount of CaMg(CO3)2 left in the sample obtained after 1000 ppm to 250 ppm. It is believed that the silver NPs can
2 h, which corresponds well with the EDX spectrum (Fig. 4b). bind with the thiol groups in proteins,3840 interact with the
Fig. 4c exhibits that the sample obtained at 4 h possesses a bacterial membranes,41 and this subsequently results in DNA
good spherical morphology. There are no impurities in the becoming more condensed. However, the specific reason for
composite when the reaction time was extended to 8 h (Fig. the antibacterial properties is that the silver NPs are released
S9b, ESI3) but many irregular Ag NPs aggregated on the shell of into an aqueous solution, forming Ag+ ions. Then the Ag+ ions
the spheres (Fig. 4d). It can be seen that there are a few Ca2+ strongly bind to electron donating groups in biological
ions still remaining while the Mg2+ ions were completely molecules containing sulfur, oxygen or nitrogen.33 All these
removed. These results are consistent with the different Ksp of phenomena lead to damage or even the death of the
MgCO3 (1.0 6 1026) and CaCO3 (0.87 6 1028), and the rate of microorganisms.32 Therefore as the sample concentration
ion exchange of Ag+ with Mg2+ ions is quicker than that with rises, the Ag ion concentration increases and the antibacterial
Ca2+ ions. Additionally, the amount of Ag+ ions can be properties are also improved.
controlled by the reaction time. The SEM images show that In order to determine whether the TiO2 or SiO2 matrices
the morphology of the products will be damaged if the and/or supports improve the bactericidal activity of Ag NPs,
reaction time is too long. control experiments were carried out. Free Ag NPs of several
dozen nanometers in size, TiO2 and SiO2 hollow microspheres
9742 | RSC Adv., 2013, 3, 97399744 This journal is The Royal Society of Chemistry 2013
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Fig. 6 Optical images (I) and diameter (II) of the zones of inhibition formed by
Fig. 5 Optical images (I) and diameter (II) of the zones of inhibition formed by
using E. coli (1) and S. aureus (2) as the test bacterial spawn for (a) SiO2, (b) Ag
using E. coli (1) and S. aureus (2) as the test bacterial spawn for (a) TiO2, (b) Ag
NPs, (c) the Ag/SiO2 composite.
NPs, and (c) the Ag/TiO2 composite.
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